Phosphinidynetrimethanol triacetate and its application to cellulosicmaterials

ABSTRACT

PHOSPHINIDYNETRIMETHANOL TRIACETATE WAS PREPARED BY REACTING TETRAKIS(HYDROXYMETHYL)PHOSPHONIUM CHLORIDE WITH ACETIC ANHYDRIDE IN PYRIDINE AT ROOM TEMPERATURE. COTTON AND OTHER CELLULOSIC TEXTILES WERE TREATED WITH THE PRODUCT PRODUCED BY THE NEW PROCESS AND FOUND FLAME RETARDANT.

PHOSPHINIDYNETRIMETHANOL AND ITS APPLICATION TO CELLULOSIC MATERIALS Sigred B. Lanoux, Lafayette, Samuel E. Ellzey, Jr., New Orleans, and George L. Drake, Jr., and Wilson A. Reeves, Metairie, La., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Filed Aug. 21, 1970, Ser. No. 66,084

rm. Cl. D06m 13/34 us. Cl. s 1s9 5 Claims ABSTRACT OF THE DISCLOSURE Phosphinidynetrimethanol triacetate was prepared by reacting tetrakis(hydroxymethyl)phosphonium chloride with acetic anhydride in pyridine at room temperature. Cotton and other cellulosic textiles were treated with the product produced by the new process and found flam retardant. 7

A non-exclusive, irrevocable, royalty-free license in the invention herein described throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to phosphinidynetrimethanol triacetate, to the preparation thereof, and to a process for imparting improved physical and chemical properties to cellulosic textiles by the treating of said cellulosic textiles with the organophosphorous compound of this invention. More specifically this invention relates to the preparation of a known compound by a new method, and to the utilization of this compound in textile applications which would yield goods with fire retardance and other useful properties.

The main objective of the instant invention is to provide a new method of preparing phosphinidynetrimethanol triacetate.

A second object of the invention is to provide a process for imparting to cotton and other cellulosic textiles improved fire retardance.

Phosphinidynetrimethanol triacetate was previously prepared by a reaction between tetrakisl h'ydroxymethyl) phosphonium chloride (THPC) and acetic anhydride in glacial acetic acid at 70-80 C. under a purified nitrogen atmosphere using concentrated H 80 as a catalyst to form tetrakis(acetoxymethyl)phosphonium chloride. This compound was neutralized with an aqueous solution of NaOH to form phosphinidynetrimethanol triacetate (Zhur. Obshch. Khim. 37, 2747). Addition of an aqueous solution of NaOH is a sensitive step in that the compound is easily oxidized to phosphinylidynetrimethanol triacetate.

According to the method of the instant invention phosphinidynetrimethanol triacetate is prepared directly in a one-step reaction and the sensitive step which involves the use of NaOH is avoided.

In the course of our investigations we have found that phosphinidynetrimethanol triacetate can be prepared by reacting THPC with acetic anhydride in pyridine at room temperature. The reaction of THPC with acetic anhydride is carried out by slowly adding acetic anhydride to a pyridine solution of THPC.

It was noted that phosphinidynetrimethanol triacetate became oxidized during storage in the presence of air to phosphinylidynetrimethanol triacetate to the extent of 30% in ten days.

The reaction with cellulosic material takes place in an 3,725,001 dented Apr. 3, 1973 undefined manner when a 20 weight percent solution of phosphinidynetrimethanol triacetate in dimethylform- TRIACETATE amide is padded on the cellulosic material and the material is dried in an oven, at C. for 5 minutes.

Cotton fibers, regenerated cotton fibers, paper, or other cellulosic materials are suitable for this invention. Cotton fiber is the preferred material, and may be in the form of fibers, sliver, yarn or fabric, but yarn or fabric is preferred.

The following examples illustrate procedures that have been used successfully in carrying out the invention. Cotton fabrics which have been treated by process of this invention were tested by standard methods recommended by the American Association of Textile Chemists and Colorists. Fabric combustibility tests were conducted accordin to AATCC test method 34-1966.

EXAMPLE 1 Preparation of phosphinidynetrimethanol triacetate Tetra-kis(hydroxymethyl)phosphonium chloride (303 g., 1.59 moles) was dissolved in 1800 ml. of pyridine. Acetic anhydride (727 g., 7.13 moles) was slowly added while the reaction mixture was stirred. No external source of heat was used and the reaction mixture never exceeded 40 C. The reaction mixture was stirred overnight. Volatile components of the reaction mixture were removed by distillation under vacuum. The oily residue was washed with water to remove starting materials and undesired water-soluble products. The brown oil which separated Was dried with anhydrous sodium sulfate and distilled under vacuum to give 393 g. of colorless product for a 39% yield. The boiling point of 138 C. at 0.275 mm. was recorded. Analytical: C H O P calculated C, 43.18; H, 6.06; P, 12.39. Found: C, 43.06; H, 6.16; P, 12.02.

A proton N.M.R. spectrum taken using a Varian A60A spectrometer confirmed that the product dissolved in acetone-d was pure by exhibiting only peaks related to the compound, a methyl singlet at 124 c.p.s. and a methylene doublet at 276.5 c.p.s. (J :5 c.p.s.). No other peaks were observed. 1

The compound is soluble in acetone, pyridine and dimethylformamide.

EXAMPLE 2 Demonstration of fire resistance of cotton fabric treated with phosphinidynetrimethanol triacetate A piece of cotton fabric approximately 12 inches by 12 inches (9.9 g.) was padded with an acetone (other solvents can be used) solution containing 15 weight percent phosphinidynetrimethanol triacetate and dried in an oven at 85 C. for five minutes. The treated fabric weighed 13.1 g. The partially crosslinked fabric was tested for flame retardance according to AATCC test method 34-1966. There was no afterglow and the fabric stopped *buming before the gas burner was extinguished. The aver age char length was 4-5 inches.

EXAMPLE 3 match flame was removed the flame of the paper extinguished itself.

We claim: 1, A process for imparting flame retardance to a cell-ulosic textile, comprising (a) impregnating the cellulosic textile with a solution containing about 15% by Weight of phosphinidynetrimethanol triacetate, dissolved in a solvent selected from the group consisting of acetone, pyridine, and dimethylformamide, and (b) drying the wet impregnated cellulosic textile for about 5 minutes at about 85 C. 2. A flame retardant cellulosic textile produced by the process of claim 1.

UNITED STATES PATENTS 4/1970 Tesoro et al. 8120 3/1966 Hammann et al. 260-488 J MURRAY KADZ, Primary Examiner T. -G. DAVIS, Assistant Examiner U.S. Cl. X.R

3. The process of claim 1 wherein the solvent is ace- 15 P 120; 117 136, 143 R, 144, 154; PP 

